Highly protonated hydronium and peroxymonosulfuric acid as a sanitizing solution

ABSTRACT

A water-based, alcohol-free, skin and hard surfaces sanitizing solution with a natural skin softener, where the nature of the biocidal enhancer used in the process of making the solution significantly increases efficacy while simultaneously enabling much more economical manufacturing, processing and transportation of the product. As the present solution is water-based, no further moisturizing additives are required, and those with sensitive skin, diabetes, allergies or religious beliefs are able to use the product without concern.

PRIORITY CLAIM AND RELATED APPLICATIONS

This continuation-in-part application claims the benefit of priorityfrom application U.S. Ser. No. 14/926,148 filed Oct. 29, 2015. Saidapplication is incorporated by reference in its entirety.

FIELD OF THE INVENTION

In one aspect, the invention relates to a solution including hydronium,sulfuric acid and hydrogen peroxide effective as a biocide applicable toboth skin and hard surfaces.

In one aspect, the invention relates to an unsubstituted quaternaryammonium salt that is an effective biocide in combination with agermicidal/bactericidal ingredient, alkyl-dimethyl-benzyl-ammoniumchloride (Benzalkronium Chloride or BAC) and carbamide peroxide(CH₆N₂O₃).

In one aspect, the invention describes a desirable effect of thechemistry combination where the creation of hydronium ions are known tomediate chemical reactions by attaching themselves to the hydrophilicends of molecules, specifically sites with partial negative charges orrich in electron density. The formation of an adduct, for sterichindrance where adding carbamide to the existing molecular chain willform a lightly bonded bi-molecule chain making the quaternary ammoniasalt larger and more difficult to penetrate the skin flora whilemaintaining its germicidal functionality. The described unsubstitutedquaternary ammonium salt composition with other ingredients has beenshown to be effective in testing against E-coli, Salmonella,Pseudomonas, Listeria, H1 N1, NDM1, Clostridium Difficile or c-Difficilespores, Rhinovirus, MRSA and a wide range of other bacteria and viruses,molds and spores.

Other additives such as scents, humectants, antifungal,anti-inflammatory, cicatrizants and hemostatic agents can be added tothe chemistry combination to promote healing as well as other medicinalbenefits.

BACKGROUND OF THE INVENTION

Hand sanitizers have been marketed and sold for decades. However, nearlyall sanitizers use alcohol at a minimum of 62% concentration as both anantiseptic and a drying agent. According to Center for Disease Control(CDC) recommendations, a hand sanitizer should contain at least 60%alcohol by volume in order to be effective. Alcohol is harsh on theskin, and also is not recommended for use by people with diabetes as itcan dramatically affect blood glucose readings. Certain religiousbeliefs restrict the use of alcohol on the hands and providing anon-alcohol-based hand sanitizer with effective killing rates addressesproblem for a large community.

Alcohol-free hand sanitizers are available, but their effectiveness islimited by the number of active ingredients allowed under the FDA 1974Tentative Final Monograph. Thus, it is necessary to find an ingredient,or combination of ingredients, that can significantly enhance theallowed biocides from the Monograph.

The FDA requirement for hand sanitizers must include active ingredientfrom a list identified in the FDA 1978 Monograph. One specific biocidelisted in the Monograph is Benzalkronium Chloride (BAC) that acts as asanitizer to disrupt the cellular membrane of micro-organisms. Thebiocide activity of BAC is enhanced by the action of the long chainsubstitutes, acting as solvents of the lipid (or other soluble) parts ofthe cellular membrane. This event disrupts the integrity of the cellularmembrane causing the outflow of the intracellular liquid. The additionof a mineral acid as H₂SO₄ lowers the pH of the system, leading to theformation of hydronium ions.

Hydronium ions are known to mediate chemical reactions by attachingthemselves to the hydrophilic ends of molecules, specifically sites withpartial negative charges or rich in electron density. H+ will bonddisrupting the general characteristics of the lipid while the long chainof BAC will solvate the hydrocarbon chain.

In addition, the solution may contain other ingredients not listed asactive by the FDA and may include but not limited to naturalmoisturizers such as carbamide. The described unsubstituted quaternaryammonium salt composition is compatible with different aromas andfragrances, such as Rose Water, Witch Hazel, Lavender, Lilac and is notlimited by one or more volatilized chemical compounds that can be addedto the solution at a very low concentration that stimulates the humanolfactory senses.

Carbamide is also highly water-soluble due to its ability to formmultiple hydrogen bonds with the low pH hydronium ions in the chemistrycomposition. The natural conditioning properties of carbamide, alsocalled urea peroxide, urea hydrogen peroxide (UHP), and percarbamide, isan adduct of hydrogen peroxide and urea and is similar to hydrogenperoxide as an oxidizer. Carbamide has several other applications. Inveterinary medicine, for instance, it is used as a topical antisepticand a diuretic.

Carbamide appears as a white crystalline solid which dissolves in waterto give free hydrogen peroxide and is readily available with thesolubility of commercial samples varying from 0.05 g/ml to more than 0.6g/ml. The chemical formula is CH₆N₂O₃. As a natural skin conditioner theallergic reactions by users to dyes and chemicals found in readilyavailable alcohol-based hand sanitizers is avoided. The use of low dosesof Carbamide has shown to reduce the effects of acne and psoriasis onthe skin without damaging side effects found in some medications. TheApplicant further discovered that a mixture of carbamide and hydroniumaids in creating amino acids that are the building blocks for proteinsto promote healing in wound beds. These proteins create an immune systemthat identifies and neutralizes pathogens such as bacteria and viruses.In one embodiment, carbamide is supplied in the amount of from about0.004% to about 4% by weight of the total weight of the skin sanitizingand wound healing solution. In some instances, carbamide is better knownas urea (CH₄N₂O). Carbamide reacts with the organic acid in the presentprotonated solution and creates uronium hydrogen sulfate (CH₄N₂O.H₂O₄S).This solution differs from urea hydrogen peroxide (UHP or CO(NH₂)₂.H₂O₂)found in tooth paste. Uronium Hydrogen Sulfate promotes rehydration ofthe skin and wound healing along with the water in the solution. Inwound healing, the key elements of an amino acid are carbon, hydrogen,oxygen, and nitrogen. These are created by a chemical chain ofCH₄N₂O.H₂O₄S in the solution though other elements are found in theside-chains of certain amino acids.

As documented in Wikipedia website, Aloe vera is now widely used onfacial tissues, where it is promoted as a moisturizer and/oranti-irritant to reduce chafing of the nose of users suffering hay-feveror cold. Aloe vera is also used for soothing the skin, and keeping theskin moist to help avoid flaky scalp and skin in harsh and dry weather.Aloe vera may also be used as a moisturizer for oily skin. Aloe vera canbe easily added to the described highly protonated, low pH,nondermathropic solution as a moisturizer. Taspine is an alkaloidextracted from trees of Croton (family Euphorbiaceae) of the westernAmazon region that has been used by natives and others as a vulneraryagent when purified from the tree sap. Some testing and data suggestthat taspine promotes early phases of wound healing in a dose-dependentmanner with no substantial modification thereafter. Its mechanism ofaction is probably related to its chemotactic properties on fibroblastsand is not mediated by changes in extracellular matrix. Additionally,Taspine can be added to the described highly protonated, low pH,nondermathropic solution as a natural moisturizer and wound healingingredient.

SUMMARY OF THE INVENTION

The described invention of using a base chemistry where a highconcentration of Hydronium Ions is created as a base chemistry whereother ingredients described in the invention forms a composition thatboth reduces bacteria on the skin and a natural moisturizer withextended protection up to forty-eight hours after application to theskin. As a result, the described skin sanitizing solution both sanitizesand moisturizes the skin on contact without the addition of harshchemicals, such as alcohol, and without the need for skin conditioningadditives that may contain objectionable chemistry, dyes and perfumes.

DETAILED DESCRIPTION OF THE INVENTION

The term “about” is used herein to mean approximately, roughly, around,or in the region of. When the term “about” is used in conjunction with anumerical range, it modifies that range by extending the boundariesabove and below the numerical values set forth. In general, the term“about” is used herein to modify a numerical value above and below thestated value by a variance of 20 percent up or down (higher or lower).

In one aspect, the invention is an unsubstituted quaternary ammoniumsalt composition with other ingredients that comprises a compositionthat is non-flammable, alcohol-free, non-stinging, highly protonated,and nondermatropic. The composition has a very high hydronium protoncount and is created by a process involving the blending of a premixthat comprises a highly protonated, non-corrosive, nondermatropichydronium carrier and a biocide, added to a predetermined quantity ofwater until it dissolves. In one embodiment, the present hydroniumcomprises a proton count of between about 4×10²⁰ and about 5.8×10²³. Inone embodiment, the present hydronium disposed at a pH of from about 1.5to about 1.8 is found suitable for hand sanitizing or any applicationsrequiring contact with human skin while the preferable pH range for hardsurface sanitizing or any applications where contact with human skin isnot a concern, ranges from about 0.5 to about 1.2. In one embodiment,the biocide further comprises one or more quaternary ammonium compounds.

The described unsubstituted quaternary ammonium salt composition withother ingredients comprises a blend of an inorganic acid, a sulfate, andwater or a blend of organic acid, a sulfate, and water. The quaternaryammonium compound is selected from one or more of the group consistingof Benzalkonium Chloride, Cetylpyridinium Chloride, Silver Chlorideadsorbed to titanium dioxide (initially notified under silver chloride),Cetalkonium chloride, Benzyldimethyl (octadecyl) ammonium chloride,Miristalkonium chloride, Dimethyldioctylammonium chloride, Hydrogenchloride/hydrocholoric acid, Silver Chloride, Dodecylguanidinemonohydrochloride, Bromine chloride, Dimethyloctadecyl[3-(trimethoxysilyl) propyl] ammonium chloride,Decyldimethyloctylammonium chloride, Benzyldimethyloleylammoniumchloride, Dimethyltetradecyl[3-(trimethoxysilyl)propyl]ammoniumchloride, benzylcoco alkyldimethyl chlorides, dicocoalkyl dimethyl,chlorides, bis(hydrogenated tallow alkyl) dimethyl chlorides,benzyl-c8-18-alkyldimethyl chlorides, benzyl-c12-18-alkyldimethylchlorides, di-C6-12-alkyldimethyl chlorides, benzyl-c8-16-alkyldimethylchlorides, di-c8-10-alkyldimethyl chlorides, benzyl-C10-16-alkyldimethylchlorides, Octenidine dihydrochloride di-C8-18 alkyldimethyl, chlorides,benzyl-C12-14-alkyldimethyl chlorides,C12-14-alkyl[(ethylphenyl)methyl]dimethyl chlorides.

The inorganic acid is selected from one or more of the group consistingof sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boricacid, hydrofluoric acid, hydrobromic acid.

The organic acid selected from one or more of the group consisting oflactic acid, acetic acid, formic acid, citric acid, oxalic acid, uricacid.

The solution may further comprise a skin permeation enhancer orconditioner selected from one or more of the group consisting of naturalcomponents and vitamins, minerals, urea or anti-oxidants to enhance thecomposition's natural skin moisturizing and protection against thespread of acne and psoriasis.

A thickener may be added to make a gel formula solution. The thickeneris selected from one or more of the group consisting of Xanthan gum,Alginic acid, Sodium alginate, Ammonium alginate, Calcium alginate,Propylene glycol alginate, Propane-1,2-diol alginate, Agar, Carrageenan,Processed euchuema seaweed, Furcelleran, Aribinogalactan larch gum,Locust Bean (carob gum), Oat gum, Guar gum, Tragacanth, Acadia Gum (GumArabic), Karaya gum, Tara Gum, Gellan gum, Sorbitol, Mannitol, Glycerol,Konjac, Konjac gum, Polyoxethylene (8) sterate, Polyoxyl 8 stearate,Polyoxyethylene (40) stearate, Polyoxyethylene (20) sorbitan monolaurate(polysorbate 20), Polysorbate 80, Polyoxethylene sorbitan mono-oleate,Polyoxethylene sorbitan monopalminate, Polysorbate 40, Tween 40,Polyxethylene sorbitan monostearate, Polysorbate 60, Tween 60,Polyoxyethylene-20-sorbitan tristearate, Polysorbate 65, Tween 65,Pectin, Amidated pectin, Gelatine, Ammonium phosphatides, Sucroseacetate isobutyrate, SAIB, Sucrose diacetate hexaisobutyrate, Glycerolesters of wood rosins, Sodium and potassium pyrophosphates,Diphosphates, Ammonium phosphate (diabasic and monobasic), Sodium andpotassium triphosphate, Triphosphate, Sodium and potassiumpolyphosphates, Polyphosphates, Beta-cyclodextrine, Cellulose(microcrystalline and powdered), Methyl cellulose, Ethyl cellulose,Hydroxypropyl cellulose, Hydroxypropyl methyl cellulose,Methylethylcellulose, Carboxymethyl cellulose, Sodium carboxymethylcellulose, Crosslinked sodium carboxymethyl cellulose, Sodium caseinate,Magnesium stearate, Sodium, potassium and calcium salts of fatty acids,Magnesium salts of fatty acids, Mono- and diglycerides of fatty acids(glyceryl monostearate, glyceryl distearate), Acetic and fatty acidesters of glycerol, Acetic acid esters of mono- and diglycerides offatty acids, Lactic and fatty acid esters of glycerol, Lactic acidesters of mono- and diglycerides of fatty acids, Citric and fatty acidesters of glycerol, Citric acid esters of mono- and diglycerides offatty acids, Tartaric and fatty acid esters of glycerol, Tartaric acidesters of mono- and diglycerides of fatty acids, Diacetyltartaric andfatty acid esters of glycerol, mon- and diacetyl tartaric acid esters ofmonoand diglycerides of fatty acids, Mixed acetic and tartaric acidesters of mono- and diglycerides of fatty acids, Sucrose esters of fattyacids, Sucroglycerides, Polyglycerol esters of fatty acids, Polyglycerolesters of interesterified ricinoliec acid, Propylene glycol mono- anddi-esters, Propane 1,2-Diol esters of fatty acids, Lactylated fatty acidesters of glycerol and propane-1,2-diol, Thermally oxidized soy bean oilinteracted with mono- and diglycerides of fatty acids, Dioctyl sodiumsulphosuccinate, Sodium oleyl or stearoyl lactylatestearoyl-2-lactylate, Calcium stearoyl-2-lactylate, Stearyl tartrate,sorbitan monostearate, Sorbitan tristearate, Span 65, Sorbitanmonolaurate, Span 20, Sorbitan mono-oleate, Span 80, Sorbitanmonopalmitate, Span 40.

The unsubstituted quaternary ammonium salt created by the invention wastested by an independent laboratory and the results recorded for eachmicrobe studied. It is important to note that alcohol-based handsanitizers with or without the active ingredient BZK does not offer thesame results against MRSA, c-Difficile spores, H1N1.

Untreated Average Number Percent Microbe Control Recovered ReductionMRSA (30 Seconds) 1.7 × 10⁵ 3.3 × 10⁰ 99.998% MRSA (180 Seconds) 1.7 ×10⁵ <1.0 × 10⁰  99.999% c-Difficile Trial 1 3.3 × 10³ <1.00 99.97%spores Trial 2 3.3 × 10³ <1.00 99.97% Trial 3 3.3 × 10³ <1.00 99.97%Trial 4 3.3 × 10³ <1.00 99.97% Trial 5 3.3 × 10³ <1.00 99.97% NDM-1Trial 1 9.6 × 10⁵ <5.0 99.9995% Trial 2 9.6 × 10⁵ <5.0 99.9995% Trial 39.6 × 10⁵ <5.0 99.9995% Trial 4 9.6 × 10⁵ <5.0 99.9995% Trial 5 9.6 ×10⁵ <5.0 99.9995% Rhinovirus 39 6.7 × 10⁵ 4.8 × 10⁰ 99.993% Influenza A(H1N1) 3.1 × 10⁴ <2.2 99.993% PRD-1 Bacteriophage 2.0 × 10⁴ 4.3 × 10⁰99.98% E. Coli 9.10 × 10⁵  <0.5 99.9999% E. Coli (Dry Test) 5.6 × 10⁴3.7 × 10² 99.3% Salmonella Enterica 1.1 × 10⁶ <0.5 99.9999% SalmonellaEnterica 1.6 × 10⁵ 1.6 × 10² 99.9% (Dry Test)

This product is manufactured according to FDA Tentative Final Monograph(1974, 1978, 1991, 1994, 2002). All testing is performed by anindependent registered laboratory, according to test methods describedin AOAC Official Method 961.02 (Germicidal Spray Products asDisinfectants), ASTME 1053-97 (Standard Test Method for Efficacy ofVirucidal Agents Intended for Inanimate Surfaces), and from ASTME2111-00 (Standard Quantitative Carrier Test Method to Evaluate theBactericidal, Fungicidal, Mycobactericidal and Sporicidal Potencies ofLiquid Chemical Germicides). The FDA does not specify testing protocolsfor this product. Copies of full reports are available upon request.

The solution also was graded minimally irritating at 2.8 (non-irritant)on the standardized Draize Test scale where 0 is non-irritating and 110is severe/extreme where skin damage will occur.

According to Wikipedia website, the Draize Test is an acute toxicitytest devised in 1944 by the Food and Drug administration (FDA)toxologists John H. Draize and Jacob M. Spines. Initially used fortesting cosmetics, the procedure involves applying 0.5 mL or 0.5 g of atest substance to the eye or skin of a restrained, conscious animal, andthen leaving it for set amount of time before rinsing it out andrecording its effects. The animals are observed for up to 14 days forsigns of erythema and edema in the skin test, and redness, swelling,discharge, ulceration, hemorrhaging, cloudiness, or blindness in thetested eye. The test subject is commonly an albino rabbit, though otherspecies are used too, including dogs. The animals are euthanized aftertesting if the test renders irreversible damage to the eye or skin.Animals may be re-used for testing purposes if the product tested causesno permanent damage. Animals are typically reused after a “wash out”period during which all traces of the tested product are allowed todisperse from the test site. The FDA supports the test, stating that “todate, no single test, or battery of tests, has been accepted by thescientific community as a replacement [for] . . . the Draize test”

Preferred Embodiment

In one embodiment, the invention includes the use of the describedunsubstituted quaternary ammonium salt composition with otheringredients which are fully incorporated herein by reference, as theIonic Carrier premix. In this embodiment, 10 grams of the describedhighly protonated, low pH, nondermathropic solution are blended in a 1:2ratio with water, by weight. This blend is then added to 5.5 grams ofBenzalkonium Chloride, mixed with 3 grams of Urea, and 481.5 grams ofwater.

The amount of thickener can vary, depending upon the final intended use.0.5% to 1% xanthan gum gives a good consistency for a hand gel. Theformula is a composition, which is a highly protonated, supercharged,non-corrosive liquid proton suspending composition.

The manufacturing process to create the described unsubstitutedquaternary ammonium salt with is well known and beginning as early asthe 1980's various chemists and inventors have experimented with thenature of this reaction of adding acid to the water. Generally speaking,these reactions and resulting compounds have lacked stability and themanufacturing process was extremely expensive for commercialization.However, this invention has created a compound reaction of the severalelements for making the described unsubstituted quaternary ammonium saltcomposition with other ingredients of adding sulfuric acid of at least88% purity in a controlled manner to water while vigorously stirring andagitating said solution to control the temperature of the exothermicreaction.

In one embodiment, another sanitizing solution suitable for sanitizingboth skin and hard surface is provided. As used herein, a hard surfaceis defined as an inanimate, non-porous surface, e.g., but not limitedto, stainless steel, glass, aluminum, epoxy, enamel, acrylic, Mipolam®,vinyl, hardwood, melamine covered wood, plastic, Plexiglas®, chromium,kitchen surfaces, bathroom surfaces, tub surfaces and tile surfaces. Inproducing this solution, a base solution of hydronium having a protoncount between about 4×10²⁰ and about 5.8×10²³ is first provided. Thissolution is then mixed with an inorganic acid, e.g., sulfuric acid(H₂SO₄), hydrogen peroxide (H₂O₂) and water to yield peroxymonosulfuricacid (H₂SO₅) and hydronium. In one embodiment, a 35% active hydrogenperoxide (H₂O₂) is added to the base solution in a (equilibrium)reaction stoichiometry at 1:1. For example, a solution containing 0.181grams of sulfuric acid (H₂SO₄) will require 0.0628 grams or 1/35 gramsof hydrogen peroxide (H₂O₂) to produce peroxymonosulfuric acid at a pHof 0.7. The balanced chemical equation for the reaction between sulfuricacid and hydrogen peroxide can be written as:

Under the condition of constant volume and using the obtainedfirst-order forward and reverse rate constants k_(f) and k_(r), thevalue of K_(eq) at 298 K is about 2.4×10⁵. As a result, the formation ofperoxymonosulfuric acid (H₂SO₅(aq)) is highly favored under typicalambient conditions from mixtures of aqueous solutions of sulfuric acidand hydrogen peroxide. In one embodiment, additional sulfuric acid isadded to provide unreacted sulfuric acid to enhance the efficacy of themixture in certain applications. Other suitable inorganic acids include,but not limited to hydrochloric acid, nitric acid, phosphoric acid,boric acid, hydrofluoric acid and hydrobromic acid. Due to its very highreactivity the standard reduction potential of peroxymonosulfuric acidis difficult to measure. The potassium salt of this peracid is known tohave a reduction potential of +1.85 Volts vs. the standard hydrogenelectrode, placing it higher in reduction potential than most aqueousoxidants. It is likely that aqueous solutions of the free peracid wouldat least transiently possess even higher standard reductions potentials.A thickener, as disclosed elsewhere herein, can also be applied to thisembodiment to facilitate its application to skin or hard surfaces.

Several tests were carried out to examine the efficacies of the presentsolution on skin and a hard surface. The resultant solution includingperoxymonosulfuric acid is observed to attacks germ cells (includingc-Difficile spores) without damaging the skin and integrity of thesurface or equipment. In preparing for tests on hard surface,c-Difficile spores production and purification were performed accordingto EPA SOP MB-28-04: Production of c-Difficile spores for use in theefficacy evaluation of antimicrobial agents. The method was based onASTM Standard E2839-11 for producing standardized spore suspensions ofc-Difficile. Tests were carried out according to EPA SOP MB-31-03. Thisquantitative method is used to assess the sporicidal efficacy ofdisinfectants against c-Difficile spores (ATCC 43598) on inanimate, hardand non-porous surfaces. Each soiled sample of 5% Tripartite was treatedwith the present resultant solution including peroxymonosulfuric acidand observed after a period of treatment to show its efficacy againstc-Difficile spores.

It should be understood that the preceding is merely a detaileddescription of one or more embodiments of this invention and thatnumerous changes to the disclosed embodiments can be made in accordancewith the disclosure herein without departing from the spirit and scopeof the invention. The preceding description, therefore, is not meant tolimit the scope of the invention. Rather, the scope of the invention isto be determined only by the appended claims and their equivalents.

1. A sanitizing solution comprising hydronium having a proton countbetween 4×10²⁰ and 5.8×10²³, inorganic acid, Hydrogen peroxide andwater.
 2. The sanitizing solution according to claim 1, wherein theinorganic acid is sulfuric acid.
 3. The sanitizing solution according toclaim 1, further comprising a thickener configured to make a gel formulaof the solution.
 4. The sanitizing solution according to claim 3,wherein the thickener is Xanthan gum.
 5. A sanitizing solutioncomprising hydronium having a proton count between 4×10²⁰ and 5.8×10²³,sulfuric acid, hydrogen peroxide of about 35% by weight of the weight ofsaid sulfuric acid and water.
 6. The sanitizing solution according toclaim 5, further comprising a thickener configured to make a gel formulaof the solution.
 7. The sanitizing solution according to claim 6,wherein
 8. A sanitizing solution comprising: a peroxymonosulfuric acidformed by mixing water, sulfuric acid, hydrogen peroxide of about 35% byweight of the weight of said sulfuric acid in hydronium having a protoncount between 4×10²⁰ and 5.8×10²³.
 9. The sanitizing solution accordingto claim 8, further comprising a thickener configured to make a gelformula of the solution.
 10. The sanitizing solution according to claim9, wherein the thickener is Xanthan gum.